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Title: Directed Gas-Phase Synthesis of Triafulvene under Single-Collision Conditions

Abstract

The triafulvene molecule (c-C4H4)—the simplest representative of the fulvene family—has been synthesized for the first time in the gas phase through the reaction of the methylidyne radical (CH) with methylacetylene (CH3CCH) and allene (H2CCCH2) under single-collision conditions. The experimental and computational data suggest triafulvene is formed by the barrierless cycloaddition of the methylidyne radical to the p-electron density of either C3H4 isomer followed by unimolecular decomposition through elimination of atomic hydrogen from the CH3 or CH2 groups of the reactants. The dipole moment of triafulvene of 1.90 D suggests that this molecule could represent a critical tracer of microwaveinactive allene in cold molecular clouds, thus defining constraints on the largely elusive hydrocarbon chemistry in lowtemperature interstellar environments, such as that of the Taurus Molecular Cloud 1 (TMC-1).

Authors:
ORCiD logo [1];  [1];  [1];  [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Univ. of Hawaii at Manoa, Honolulu, HI (United States)
  2. Samara National Research Univ., Samara (Russian Federation); Florida International Univ., Miami, FL (United States)
  3. Florida International Univ., Miami, FL (United States)
Publication Date:
Research Org.:
Univ. of Hawaii at Manoa, Honolulu, HI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1603226
Alternate Identifier(s):
OSTI ID: 1560246
Grant/Contract Number:  
FG02-03ER15411; FG02-04ER15570
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 58; Journal Issue: 43; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Thomas, Aaron M., Zhao, Long, He, Chao, Galimova, Galiya R., Mebel, Alexander M., and Kaiser, Ralf I.. Directed Gas-Phase Synthesis of Triafulvene under Single-Collision Conditions. United States: N. p., 2019. Web. https://doi.org/10.1002/anie.201908039.
Thomas, Aaron M., Zhao, Long, He, Chao, Galimova, Galiya R., Mebel, Alexander M., & Kaiser, Ralf I.. Directed Gas-Phase Synthesis of Triafulvene under Single-Collision Conditions. United States. https://doi.org/10.1002/anie.201908039
Thomas, Aaron M., Zhao, Long, He, Chao, Galimova, Galiya R., Mebel, Alexander M., and Kaiser, Ralf I.. Wed . "Directed Gas-Phase Synthesis of Triafulvene under Single-Collision Conditions". United States. https://doi.org/10.1002/anie.201908039. https://www.osti.gov/servlets/purl/1603226.
@article{osti_1603226,
title = {Directed Gas-Phase Synthesis of Triafulvene under Single-Collision Conditions},
author = {Thomas, Aaron M. and Zhao, Long and He, Chao and Galimova, Galiya R. and Mebel, Alexander M. and Kaiser, Ralf I.},
abstractNote = {The triafulvene molecule (c-C4H4)—the simplest representative of the fulvene family—has been synthesized for the first time in the gas phase through the reaction of the methylidyne radical (CH) with methylacetylene (CH3CCH) and allene (H2CCCH2) under single-collision conditions. The experimental and computational data suggest triafulvene is formed by the barrierless cycloaddition of the methylidyne radical to the p-electron density of either C3H4 isomer followed by unimolecular decomposition through elimination of atomic hydrogen from the CH3 or CH2 groups of the reactants. The dipole moment of triafulvene of 1.90 D suggests that this molecule could represent a critical tracer of microwaveinactive allene in cold molecular clouds, thus defining constraints on the largely elusive hydrocarbon chemistry in lowtemperature interstellar environments, such as that of the Taurus Molecular Cloud 1 (TMC-1).},
doi = {10.1002/anie.201908039},
journal = {Angewandte Chemie (International Edition)},
number = 43,
volume = 58,
place = {United States},
year = {2019},
month = {7}
}

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Cited by: 3 works
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Figures / Tables:

Scheme 1 Scheme 1: Molecular structures and symmetries of triafulvene 1, pentafulvene 2, heptafulvene 3, and nonafulvene 4.

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Works referenced in this record:

Ueber Ketonreactionen bei dem Cyclopentadiën
journal, January 1900


4. Condensationsproducte des cyklopentadiëns
journal, January 1906


Quantum dynamical simulations for nuclear spin selective laser control of ortho - and para -fulvene
journal, July 2009

  • Belz, S.; Grohmann, T.; Leibscher, M.
  • The Journal of Chemical Physics, Vol. 131, Issue 3
  • DOI: 10.1063/1.3175800

Fulvenes, Fulvalenes, and Azulene:  Are They Aromatic Chameleons?
journal, November 2004

  • Möllerstedt, Helene; Piqueras, Mari Carmen; Crespo, Raül
  • Journal of the American Chemical Society, Vol. 126, Issue 43
  • DOI: 10.1021/ja045729c

Quantification of the (anti)aromaticity of fulvenes subject to ring size
journal, April 2008


Substituent Effects on π -Bond Delocalization of Fulvenes and Fulvalenes. Are Fulvenes Aromatic?
journal, June 2015


A Versatile Diquinane from Fulvene as a Building Block in Natural Product Synthesis. 1. A Facile Synthesis of the Iridoids Loganin and Sarracenin
journal, January 1999

  • Tai, Huo-Mu; Chang, Meng-Yang; Lee, An-Yang
  • The Journal of Organic Chemistry, Vol. 64, Issue 2
  • DOI: 10.1021/jo9817624

Recent Advances in the Chemistry of Pentafulvenes
journal, February 2017


Low-Valent Titanium-Pentafulvene Complexes - Formation of Dinuclear Titanium-Nitrogen Complexes: Low-Valent Titanium-Pentafulvene Complexes
journal, March 2005

  • Scherer, Axel; Kollak, Kay; Lützen, Arne
  • European Journal of Inorganic Chemistry, Vol. 2005, Issue 6
  • DOI: 10.1002/ejic.200400938

Pentafulvene complexes of group four metals: Versatile organometallic building blocks
journal, December 2018


Fluorescent chemosensors based on 9-cycloheptatrienylidene fluorenes (9-CHFs)
journal, January 2013

  • Hu, Binbin; Lu, Ping; Wang, Yanguang
  • New Journal of Chemistry, Vol. 37, Issue 6
  • DOI: 10.1039/c2nj41063j

Molecular Structures of Fulvalenes Derived from Methylidenecycloproparenes:  X-ray Structure Determinations and ab Initio Calculations
journal, October 1998

  • Apeloig, Yitzhak; Boese, Roland; Halton, Brian
  • Journal of the American Chemical Society, Vol. 120, Issue 39
  • DOI: 10.1021/ja973020i

Exploration of the potential energy surface of C4H4 for rearrangement and decomposition reactions of vinylacetylene: A computational study. Part I
journal, January 2006

  • Cremer, Dieter; Kraka, Elfriede; Joo, Hyun
  • Physical Chemistry Chemical Physics, Vol. 8, Issue 45
  • DOI: 10.1039/b609284e

Structures of, and charge separation in, 2,3-diphenyl-4,4-dicyanotriafulvene and 2,3-diphenylcyclopropenone
journal, October 1973

  • Ammon, Herman L.
  • Journal of the American Chemical Society, Vol. 95, Issue 21
  • DOI: 10.1021/ja00802a033

Synthesis of methylenecyclopropene
journal, June 1984

  • Billups, W. E.; Lin, Long Jin; Casserly, Edward W.
  • Journal of the American Chemical Society, Vol. 106, Issue 12
  • DOI: 10.1021/ja00324a064

Synthesis and direct observation of methylenecyclopropane
journal, June 1984

  • Staley, Stuart W.; Norden, Timothy D.
  • Journal of the American Chemical Society, Vol. 106, Issue 12
  • DOI: 10.1021/ja00324a065

A new methylenecyclopropene synthesis and the isolation of a novel methylenecyclopropene dimer
journal, February 1997


Electronic character of methylenecyclopropene: microwave spectrum, structure, and dipole moment
journal, December 1986

  • Norden, Timothy D.; Staley, Stuart W.; Taylor, William H.
  • Journal of the American Chemical Society, Vol. 108, Issue 25
  • DOI: 10.1021/ja00285a005

Photochemistry of Butatriene − Spectroscopic Evidence for the Existence of Allenylcarbene
journal, April 2000

  • Wrobel, Roman; Sander, Wolfram; Cremer, Dieter
  • The Journal of Physical Chemistry A, Vol. 104, Issue 16
  • DOI: 10.1021/jp9940147

Molecular Reaction Dynamics
book, January 2005


Exchange reactions of alkali atoms with alkali halides: a collision complex mechanism
journal, January 1967

  • Miller, W. B.; Safron, S. A.; Herschbach, D. R.
  • Discussions of the Faraday Society, Vol. 44
  • DOI: 10.1039/df9674400108

Reaction mechanism and product branching ratios of the CH + C 3 H 4 reactions: a theoretical study
journal, January 2017

  • Ribeiro, Joao Marcelo; Mebel, Alexander M.
  • Phys. Chem. Chem. Phys., Vol. 19, Issue 22
  • DOI: 10.1039/C7CP01873H

Kinetic measurements on methylidyne radical reactions with several hydrocarbons at low temperatures
journal, January 2005

  • Daugey, Nicolas; Caubet, Philippe; Retail, Bertrand
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 15
  • DOI: 10.1039/b506096f

Cyclic Versus Linear Isomers Produced by Reaction of the Methylidyne Radical (CH) with Small Unsaturated Hydrocarbons
journal, January 2009

  • Goulay, Fabien; Trevitt, Adam J.; Meloni, Giovanni
  • Journal of the American Chemical Society, Vol. 131, Issue 3
  • DOI: 10.1021/ja804200v

Photodissociation of benzene under collision-free conditions: An ab initio /Rice–Ramsperger–Kassel–Marcus study
journal, April 2004

  • Kislov, V. V.; Nguyen, T. L.; Mebel, A. M.
  • The Journal of Chemical Physics, Vol. 120, Issue 15
  • DOI: 10.1063/1.1676275

A Theoretical Study of Pyrolysis of exo -Tetrahydrodicyclopentadiene and Its Primary and Secondary Unimolecular Decomposition Products
journal, May 2018

  • Morozov, Alexander N.; Mebel, Alexander M.; Kaiser, Ralf I.
  • The Journal of Physical Chemistry A, Vol. 122, Issue 22
  • DOI: 10.1021/acs.jpca.8b02934

Valence-Shell Photoionization of C 4 H 5 : The 2-Butyn-1-yl Radical
journal, January 2019

  • Hrodmarsson, H. R.; Loison, J. -C.; Jacovella, U.
  • The Journal of Physical Chemistry A, Vol. 123, Issue 8
  • DOI: 10.1021/acs.jpca.8b11809

Quantification of the resonance stabilized C4H5 isomers and their reaction with acetylene
journal, December 2018


Reaction mechanism of soot formation in flames
journal, February 2002

  • Frenklach, Michael
  • Physical Chemistry Chemical Physics, Vol. 4, Issue 11
  • DOI: 10.1039/b110045a

Detailed modeling of soot particle nucleation and growth
journal, January 1991


Low-temperature formation of polycyclic aromatic hydrocarbons in Titan’s atmosphere
journal, October 2018


Reaction Dynamics in Astrochemistry: Low-Temperature Pathways to Polycyclic Aromatic Hydrocarbons in the Interstellar Medium
journal, April 2015


Untangling the chemical evolution of Titan's atmosphere and surface–from homogeneous to heterogeneous chemistry
journal, January 2010

  • Kaiser, Ralf I.; Maksyutenko, Pavlo; Ennis, Courtney
  • Faraday Discussions, Vol. 147
  • DOI: 10.1039/c003599h

The reactivity of ground-state carbon atoms with unsaturated hydrocarbons in combustion flames and in the interstellar medium
journal, April 2002

  • Kaiser, Ralf I.; Mebel, Alexander M.
  • International Reviews in Physical Chemistry, Vol. 21, Issue 2
  • DOI: 10.1080/01442350210136602

Chemistry of Energetically Activated Cumulenes—From Allene (H2CCCH2) to Hexapentaene (H2CCCCCCH2)
journal, February 2008